trans-Di­aqua(2,2'-bi­quinoline-N,N')(nitrato-O,O')­nickel(II) nitrate hydrate

The structure of the title compound, [Ni(NO₃)(C₁₈H₁₂N₂)(H₂O)₂]NO₃·H₂O, is composed of monomers with the nickel ion octahedrally coordinated to a bidentate bi­quinoline ligand, a bidentate nitrate anion and two water mol­ecules, and is stabilized by a nitrate counter-ion and a hydrate water mol­ecule. There is a fairly complex hydrogen-bonding scheme involving all the water H atoms and five different nitrate O atoms.

S1. Comment

The title compound, (I), crystallizes as [Ni(biqui)NO₃(H₂O)₂] monomers stabilized by a nitrate counter-ion and a hydrate water molecule. The complex is octahedral, the planar base of the polyhedron being defined by two N atoms from the bidentate biquinoline ligand and two O atoms from the bidentate NO₃^- anion. The apical sites are occupied by two water molecules. The main deformation of the polyhedron is due to the small nitrate bite angle of 59.47 (4)°; the bite angle of the biquinoline ligand is wider at 81.53 (5)°.

Nickel nitrates are common. There are 40 reported in the Cambridge Structural Database (CSD; Allen & Kennard, 1993), 28 of which are bidentate in an octahedral coordination. The mean values for the Ni—O distances and O—Ni—O angles in this group are 2.16 (4) Å and 59.7 (12)°, respectively, which compare fairly well with the values obtained in the present complex of 2.18 (3) Å and 59.47 (4)°. An examination of the geometries of the two different nitrate groups in the structure shows a clear inverse correlation of the N—O distances with the degree of involvement of the group in coordination, either directly to the cation or through hydrogen bonding to another O atom. Thus, in the bidentate nitrate anion denoted A, the non-coordinated O3A atom shows the shortest N—O distance of 1.2225 (16) Å. In the other two (coordinated) O atoms, there is a clear inverse trend, i.e. the longer the Ni—O bond length, the shorter the corresponding N—O bond length [Ni1—O1A 2.2065 (15) Å and N1A—O1A 1.2694 (15) Å; Ni1—O2A 2.1417 (10) Å and N1A—O2A 1.2818 (15) Å].

A similar effect seems to be present in counter-ion B, when hydrogen interactions are considered. Thus, the O2B atom is an acceptor of a stronger hydrogen bond [H1WB···O1B 1.90 (2) Å] than those in which O2B and O3B are involved [H3WA···O2B 2.00 (3) Å and H3WB···O3B2.02 (3) Å]. This correlates nicely with the nitrate N—O bond distances, viz. a longer N1B—O1B distance of 1.2648 (17) Å, and two shorter, almost equal, N1B—O2B and N1B—O3B distances of 1.2477 (17) and 1.2467 (17) Å, respectively.

These results agree with the fact that both nitrate groups modify their N—O bond lengths in order to maintain the valence over nitrogen. A simple calculation following Brown & Altermatt (1985) gave for this value as 4.82 in the case of the coordinated moiety and 4.87 in the ionic case, quite close to the expected value of 5 for nitrogen.

The organic ligand does not present anomalies in bond distances or angles, but departs somewhat from the expected planarity; the normals of the two lateral wings deviate from the normal of the coordination plane in opposite directions by 3.9 and 6.5°, and as a result, the group appears slightly twisted around the C9—C10 bond [N1—C9—C10—N2: 6.11 (19)°]. Due to the lack of steric hindrances, the ligand binds to the cation almost parallel to the basal plane (slanting angle ca 3.1°).

The only other known complex presenting a biquinoline group coordinated to Ni is [Ni(biqui)(acet)(H₂O)₂] (Freire et al., 2001), which displays a very similar type of coordination, with the bidentate nitrate being replaced by acetate and where the stabilizing agent is the unusual pentathionate ion.

The profusion of donors and acceptors for hydrogen bonding is responsible for a very complex hydrogen-bonding scheme, with all six water H atoms and five out of six nitrate O atoms taking part. Table 2 displays the most important bonds, separating them into two groups. Through the interactions in the first group, the structure organizes itself into `dimers' (Fig. 2) around the center of symmetry at (1 - x, 1 - y, 1 - z). These are the `elemental units' of the packing. Each `dimer' in turn interacts with four neighboring `dimers' (represented in Fig. 2 by sites A, A', B and B') through the hydrogen bonds listed in the second group, resulting in a robust three-dimensional structure. Finally, there are a couple of short C—H···O contacts which also make a contribution to the stabilization of the structure.

Related literature

For related literature, see: Allen & Kennard (1993); Freire et al. (2001).

S2. Experimental

The compound was obtained by chance, as a by-product in one of the many unsuccessful attempts to obtain single crystals of Ni(biqui)thiosulfate (biqui is 2,2'-biquinoline), a synthesis problem which is still unsolved. The procedure used was as follows: the biquinoline was dissolved in hot acetone, and in order to facilitate the dissolution of the inorganic salts to be added later, water was incorporated into the solution, taking care to avoid ligand precipitation. To this solution nickel, nitrate was first added, followed by sodium thiosulfate (which partially decomposed). Crystals of the product appeared after evaporation in the form of nicely shaped pale-blue prisms. The starting materials were purchased from Aldrich and used without further purification. Elemental analyses (C, H, N, S) were performed on a Carlo Erba EA 1108 instrument. Nickel was determined on a Shimadzu AA6501 spectrophotometer.

S3. Refinement

Refinement was performed with isotropic displacement parameters for H atoms and C—H = 0.899 (18)–0.973 (19) Å.

Computing details

Data collection: SMART-NT (Bruker, 1999); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1991); software used to prepare material for publication: PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).

Figures

Fig. 1. View of the unit-cell contents showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. Schematic view of the packing showing the elemental `dimeric unit' formed around the center of symmetry at (1/2, 1/2, 1/2), and the way in which it interacts with symmetry-related neighboring `dimers' (A, B, A' and B'). For clarity, the bulky biquinoline group has been idealized by the N—C—C—N loop. Heavy broken lines represent hydrogen bonds of the first group in Table 2 which define the `dimers', while dotted lines represent hydrogen bonds of the second group which link symmetry-related neighboring `dimers'. [Symmetry codes: (A) x - 1, y, z; (B) x - 0.5, -y - 1.5, z - 0.5; (A') -x + 2, -y + 1, -z + 1; (B') -x + 1.5, y - 0.5,-z + 1.5.]

trans Diaqua(biquinoline N,N')(nitrato O,O')-Nickel(II) nitrate,hydrate

Crystal data

[Ni(NO3)(C18H12N2)(H2O)2]NO3·H2O	F(000) = 1016
Mr = 493.07	Dx = 1.664 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.4250 (7) Å	Cell parameters from 971 reflections
b = 11.2156 (7) Å	θ = 12.1–23.5°
c = 20.8889 (14) Å	µ = 1.05 mm^−1
β = 94.499 (3)°	T = 110 K
V = 1967.7 (2) Å^3	Elongated prism, pale blue
Z = 4	0.64 × 0.14 × 0.08 mm

Data collection

Bruker SMART CCD 1K area-detector diffractometer	4880 independent reflections
Radiation source: fine-focus sealed tube	4290 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 8 pixels mm^-1	θmax = 28.3°, θmin = 2.0°
ω scans	h = −11→10
Absorption correction: integration (XPREP in SHELXTL; Bruker, 1999)	k = −14→14
Tmin = 0.691, Tmax = 0.921	l = −27→27
24538 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 1.308P] where P = (Fo^2 + 2Fc^2)/3
4880 reflections	(Δ/σ)max < 0.001
361 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

Experimental. The data collection nominally covered full sphere of reciprocal Space, by a combination of 5 sets of ω scans each set at different ϕ and/or 2θ angles and each scan (10 s exposure) covering 0.3° in ω. Crystal to detector distance 4.51 cm.

A highly redundant (sixfold) data set was gathered at 110 K. The structure resolution was achieved routinely by direct methods and difference Fourier, where all atoms, including H atoms, were found

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.71854 (2)	0.309418 (15)	0.513594 (8)	0.01182 (6)
N1	0.78483 (14)	0.14554 (10)	0.48170 (6)	0.0131 (2)
N2	0.59938 (14)	0.20499 (10)	0.57545 (6)	0.0136 (2)
C1	0.87359 (16)	0.12076 (12)	0.43050 (7)	0.0141 (3)
C2	0.93987 (18)	0.21489 (13)	0.39622 (7)	0.0180 (3)
H2	0.921 (2)	0.2909 (16)	0.4072 (8)	0.014 (4)*
C3	1.02937 (19)	0.19008 (15)	0.34570 (7)	0.0206 (3)
H3	1.071 (2)	0.2534 (17)	0.3226 (9)	0.019 (4)*
C4	1.05637 (19)	0.07106 (15)	0.32684 (7)	0.0211 (3)
H4	1.119 (2)	0.0568 (16)	0.2905 (9)	0.022 (5)*
C5	0.99398 (18)	−0.02163 (14)	0.35918 (7)	0.0193 (3)
H5	1.011 (2)	−0.1006 (17)	0.3471 (9)	0.023 (5)*
C6	0.90128 (17)	0.00082 (13)	0.41195 (7)	0.0160 (3)
C7	0.83592 (18)	−0.09132 (13)	0.44729 (7)	0.0175 (3)
H7	0.849 (2)	−0.1697 (17)	0.4365 (9)	0.019 (4)*
C8	0.74967 (18)	−0.06516 (13)	0.49823 (7)	0.0167 (3)
H8	0.703 (2)	−0.1252 (18)	0.5218 (9)	0.025 (5)*
C9	0.72639 (16)	0.05536 (12)	0.51467 (7)	0.0143 (3)
C10	0.63047 (16)	0.08912 (12)	0.56877 (7)	0.0143 (3)
C11	0.57405 (18)	0.00126 (13)	0.61027 (7)	0.0182 (3)
H11	0.602 (2)	−0.0795 (18)	0.6070 (9)	0.025 (5)*
C12	0.48001 (18)	0.03479 (14)	0.65764 (7)	0.0197 (3)
H12	0.441 (2)	−0.0247 (18)	0.6859 (9)	0.030 (5)*
C13	0.43677 (17)	0.15530 (14)	0.66366 (7)	0.0174 (3)
C14	0.32808 (19)	0.19479 (15)	0.70784 (7)	0.0217 (3)
H14	0.286 (2)	0.1397 (18)	0.7332 (9)	0.025 (5)*
C15	0.2839 (2)	0.31151 (16)	0.70976 (7)	0.0240 (3)
H15	0.207 (2)	0.3352 (17)	0.7368 (10)	0.026 (5)*
C16	0.3513 (2)	0.39562 (15)	0.66944 (8)	0.0231 (3)
H16	0.320 (2)	0.4771 (19)	0.6703 (10)	0.033 (5)*
C17	0.45855 (19)	0.36138 (14)	0.62704 (7)	0.0194 (3)
H17	0.498 (2)	0.4172 (17)	0.6011 (9)	0.023 (5)*
C18	0.50117 (16)	0.23994 (13)	0.62171 (6)	0.0147 (3)
N1A	0.77664 (14)	0.53075 (11)	0.49505 (6)	0.0149 (2)
O1A	0.84085 (13)	0.45064 (9)	0.46278 (5)	0.0180 (2)
O2A	0.67325 (12)	0.49408 (9)	0.53239 (5)	0.0166 (2)
O3A	0.81033 (13)	0.63638 (9)	0.49116 (5)	0.0206 (2)
N1B	0.60734 (16)	0.68543 (11)	0.70420 (6)	0.0193 (3)
O1B	0.48877 (15)	0.74625 (11)	0.68238 (5)	0.0272 (3)
O2B	0.64857 (16)	0.59727 (10)	0.67307 (6)	0.0298 (3)
O3B	0.68221 (15)	0.71398 (11)	0.75577 (6)	0.0299 (3)
O1W	0.53077 (13)	0.30913 (10)	0.44540 (5)	0.0181 (2)
H1WA	0.464 (3)	0.358 (2)	0.4462 (10)	0.033 (6)*
H1WB	0.537 (3)	0.2968 (19)	0.4059 (11)	0.035 (6)*
O2W	0.91352 (13)	0.32180 (9)	0.57848 (5)	0.0164 (2)
H2WA	0.992 (3)	0.3462 (18)	0.5619 (10)	0.028 (5)*
H2WB	0.904 (3)	0.361 (2)	0.6119 (12)	0.039 (6)*
O3W	0.89978 (16)	0.43233 (12)	0.68918 (6)	0.0256 (3)
H3WA	0.829 (3)	0.483 (2)	0.6897 (12)	0.051 (7)*
H3WB	0.875 (3)	0.377 (2)	0.7130 (13)	0.055 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01315 (9)	0.00991 (9)	0.01263 (9)	0.00043 (6)	0.00240 (6)	0.00032 (6)
N1	0.0123 (5)	0.0129 (5)	0.0139 (5)	0.0009 (4)	−0.0004 (4)	−0.0004 (4)
N2	0.0130 (5)	0.0137 (5)	0.0140 (5)	−0.0009 (4)	0.0007 (4)	0.0007 (4)
C1	0.0123 (6)	0.0156 (6)	0.0139 (6)	0.0018 (5)	−0.0013 (5)	−0.0020 (5)
C2	0.0195 (7)	0.0162 (7)	0.0185 (7)	0.0006 (5)	0.0032 (6)	−0.0023 (5)
C3	0.0197 (7)	0.0249 (8)	0.0175 (7)	−0.0008 (6)	0.0038 (6)	−0.0002 (6)
C4	0.0184 (7)	0.0290 (8)	0.0162 (7)	0.0041 (6)	0.0022 (6)	−0.0046 (6)
C5	0.0179 (7)	0.0200 (7)	0.0195 (7)	0.0055 (6)	−0.0009 (5)	−0.0073 (6)
C6	0.0139 (6)	0.0172 (7)	0.0164 (6)	0.0026 (5)	−0.0029 (5)	−0.0033 (5)
C7	0.0187 (7)	0.0121 (6)	0.0209 (7)	0.0038 (5)	−0.0045 (5)	−0.0029 (5)
C8	0.0172 (7)	0.0132 (6)	0.0188 (7)	−0.0005 (5)	−0.0034 (5)	0.0023 (5)
C9	0.0123 (6)	0.0144 (6)	0.0158 (6)	0.0002 (5)	−0.0021 (5)	0.0016 (5)
C10	0.0127 (6)	0.0154 (6)	0.0144 (6)	−0.0009 (5)	−0.0018 (5)	0.0011 (5)
C11	0.0188 (7)	0.0146 (7)	0.0208 (7)	−0.0003 (5)	−0.0004 (6)	0.0047 (5)
C12	0.0185 (7)	0.0228 (7)	0.0176 (7)	−0.0039 (6)	0.0003 (5)	0.0073 (6)
C13	0.0162 (7)	0.0222 (7)	0.0135 (6)	−0.0036 (5)	−0.0001 (5)	0.0015 (5)
C14	0.0204 (7)	0.0299 (8)	0.0153 (7)	−0.0066 (6)	0.0040 (6)	0.0017 (6)
C15	0.0200 (7)	0.0349 (9)	0.0181 (7)	−0.0020 (7)	0.0073 (6)	−0.0045 (6)
C16	0.0247 (8)	0.0234 (8)	0.0219 (7)	0.0017 (6)	0.0054 (6)	−0.0042 (6)
C17	0.0219 (7)	0.0195 (7)	0.0175 (7)	−0.0017 (6)	0.0062 (6)	−0.0005 (6)
C18	0.0127 (6)	0.0188 (7)	0.0124 (6)	−0.0016 (5)	−0.0001 (5)	−0.0004 (5)
N1A	0.0146 (6)	0.0131 (5)	0.0171 (6)	0.0007 (4)	0.0010 (4)	0.0014 (4)
O1A	0.0214 (5)	0.0150 (5)	0.0183 (5)	0.0033 (4)	0.0063 (4)	−0.0008 (4)
O2A	0.0163 (5)	0.0141 (5)	0.0201 (5)	−0.0004 (4)	0.0067 (4)	0.0009 (4)
O3A	0.0216 (6)	0.0113 (5)	0.0293 (6)	−0.0007 (4)	0.0044 (4)	0.0026 (4)
N1B	0.0236 (7)	0.0174 (6)	0.0174 (6)	−0.0020 (5)	0.0041 (5)	0.0017 (5)
O1B	0.0316 (6)	0.0287 (6)	0.0214 (6)	0.0117 (5)	0.0019 (5)	−0.0018 (5)
O2B	0.0371 (7)	0.0218 (6)	0.0293 (6)	0.0105 (5)	−0.0053 (5)	−0.0077 (5)
O3B	0.0359 (7)	0.0331 (7)	0.0198 (6)	−0.0024 (5)	−0.0032 (5)	−0.0044 (5)
O1W	0.0188 (5)	0.0185 (5)	0.0168 (5)	0.0057 (4)	−0.0001 (4)	−0.0017 (4)
O2W	0.0153 (5)	0.0171 (5)	0.0169 (5)	−0.0011 (4)	0.0025 (4)	−0.0013 (4)
O3W	0.0319 (7)	0.0256 (6)	0.0195 (6)	0.0075 (5)	0.0024 (5)	−0.0005 (5)

Geometric parameters (Å, º)

Ni1—O1W	2.0441 (11)	C11—C12	1.368 (2)
Ni1—N1	2.0476 (12)	C11—H11	0.94 (2)
Ni1—O2W	2.0507 (11)	C12—C13	1.408 (2)
Ni1—N2	2.0622 (12)	C12—H12	0.97 (2)
Ni1—O2A	2.1477 (10)	C13—C14	1.421 (2)
Ni1—O1A	2.2065 (10)	C13—C18	1.428 (2)
N1—C9	1.3390 (18)	C14—C15	1.362 (2)
N1—C1	1.3805 (18)	C14—H14	0.90 (2)
N2—C10	1.3352 (18)	C15—C16	1.413 (2)
N2—C18	1.3775 (18)	C15—H15	0.93 (2)
C1—C2	1.415 (2)	C16—C17	1.369 (2)
C1—C6	1.4242 (19)	C16—H16	0.95 (2)
C2—C3	1.373 (2)	C17—C18	1.415 (2)
C2—H2	0.899 (18)	C17—H17	0.909 (19)
C3—C4	1.415 (2)	N1A—O3A	1.2225 (16)
C3—H3	0.941 (19)	N1A—O1A	1.2694 (15)
C4—C5	1.367 (2)	N1A—O2A	1.2818 (15)
C4—H4	0.973 (19)	N1B—O3B	1.2467 (17)
C5—C6	1.423 (2)	N1B—O2B	1.2477 (17)
C5—H5	0.935 (19)	N1B—O1B	1.2648 (17)
C6—C7	1.407 (2)	O1W—H1WA	0.79 (2)
C7—C8	1.367 (2)	O1W—H1WB	0.84 (2)
C7—H7	0.917 (19)	O2W—H2WA	0.82 (2)
C8—C9	1.412 (2)	O2W—H2WB	0.83 (2)
C8—H8	0.94 (2)	O3W—H3WA	0.82 (3)
C9—C10	1.489 (2)	O3W—H3WB	0.83 (3)
C10—C11	1.4188 (19)
O1W—Ni1—N1	89.30 (5)	N1—C9—C8	122.29 (13)
O1W—Ni1—O2W	175.36 (4)	N1—C9—C10	116.21 (12)
N1—Ni1—O2W	92.93 (4)	C8—C9—C10	121.46 (13)
O1W—Ni1—N2	92.73 (5)	N2—C10—C11	122.29 (13)
N1—Ni1—N2	81.53 (5)	N2—C10—C9	116.71 (12)
O2W—Ni1—N2	91.63 (5)	C11—C10—C9	120.99 (13)
O1W—Ni1—O2A	89.43 (4)	C12—C11—C10	119.47 (14)
N1—Ni1—O2A	169.12 (4)	C12—C11—H11	118.7 (12)
O2W—Ni1—O2A	87.62 (4)	C10—C11—H11	121.8 (12)
N2—Ni1—O2A	109.33 (4)	C11—C12—C13	119.80 (14)
O1W—Ni1—O1A	91.77 (4)	C11—C12—H12	119.9 (12)
N1—Ni1—O1A	109.77 (4)	C13—C12—H12	120.3 (12)
O2W—Ni1—O1A	83.64 (4)	C12—C13—C14	122.79 (14)
N2—Ni1—O1A	167.89 (4)	C12—C13—C18	118.04 (13)
O2A—Ni1—O1A	59.47 (4)	C14—C13—C18	119.12 (14)
C9—N1—C1	119.33 (12)	C15—C14—C13	120.68 (14)
C9—N1—Ni1	112.95 (9)	C15—C14—H14	121.3 (12)
C1—N1—Ni1	127.66 (10)	C13—C14—H14	118.0 (13)
C10—N2—C18	118.94 (12)	C14—C15—C16	120.02 (15)
C10—N2—Ni1	112.22 (9)	C14—C15—H15	119.8 (12)
C18—N2—Ni1	128.80 (9)	C16—C15—H15	120.1 (12)
N1—C1—C2	120.08 (13)	C17—C16—C15	120.99 (15)
N1—C1—C6	120.74 (13)	C17—C16—H16	118.8 (13)
C2—C1—C6	119.18 (13)	C15—C16—H16	120.2 (13)
C3—C2—C1	120.01 (14)	C16—C17—C18	120.35 (14)
C3—C2—H2	120.3 (11)	C16—C17—H17	119.1 (12)
C1—C2—H2	119.7 (11)	C18—C17—H17	120.5 (12)
C2—C3—C4	121.01 (15)	N2—C18—C17	119.95 (13)
C2—C3—H3	119.3 (11)	N2—C18—C13	121.30 (13)
C4—C3—H3	119.6 (11)	C17—C18—C13	118.73 (13)
C5—C4—C3	120.22 (14)	O3A—N1A—O1A	122.67 (12)
C5—C4—H4	121.0 (11)	O3A—N1A—O2A	121.59 (12)
C3—C4—H4	118.8 (11)	O1A—N1A—O2A	115.74 (11)
C4—C5—C6	120.26 (14)	N1A—O1A—Ni1	91.04 (8)
C4—C5—H5	120.9 (12)	N1A—O2A—Ni1	93.39 (8)
C6—C5—H5	118.8 (12)	O3B—N1B—O2B	120.75 (13)
C7—C6—C5	122.53 (13)	O3B—N1B—O1B	120.31 (13)
C7—C6—C1	118.15 (13)	O2B—N1B—O1B	118.94 (13)
C5—C6—C1	119.31 (14)	Ni1—O1W—H1WA	119.8 (16)
C8—C7—C6	120.31 (13)	Ni1—O1W—H1WB	125.1 (15)
C8—C7—H7	118.8 (12)	H1WA—O1W—H1WB	104 (2)
C6—C7—H7	120.9 (12)	Ni1—O2W—H2WA	112.0 (14)
C7—C8—C9	119.16 (14)	Ni1—O2W—H2WB	117.5 (16)
C7—C8—H8	121.6 (12)	H2WA—O2W—H2WB	109 (2)
C9—C8—H8	119.3 (12)	H3WA—O3W—H3WB	107 (2)
O1W—Ni1—N1—C9	−94.13 (10)	C7—C8—C9—C10	178.63 (13)
O2W—Ni1—N1—C9	89.95 (10)	C18—N2—C10—C11	−4.0 (2)
N2—Ni1—N1—C9	−1.27 (10)	Ni1—N2—C10—C11	173.91 (11)
O2A—Ni1—N1—C9	−177.46 (19)	C18—N2—C10—C9	175.17 (12)
O1A—Ni1—N1—C9	174.23 (9)	Ni1—N2—C10—C9	−6.88 (15)
O1W—Ni1—N1—C1	83.02 (11)	N1—C9—C10—N2	6.11 (19)
O2W—Ni1—N1—C1	−92.90 (11)	C8—C9—C10—N2	−172.06 (13)
N2—Ni1—N1—C1	175.89 (12)	N1—C9—C10—C11	−174.67 (13)
O2A—Ni1—N1—C1	−0.3 (3)	C8—C9—C10—C11	7.2 (2)
O1A—Ni1—N1—C1	−8.61 (12)	N2—C10—C11—C12	2.2 (2)
O1W—Ni1—N2—C10	93.42 (10)	C9—C10—C11—C12	−176.96 (13)
N1—Ni1—N2—C10	4.53 (10)	C10—C11—C12—C13	1.7 (2)
O2W—Ni1—N2—C10	−88.18 (10)	C11—C12—C13—C14	174.15 (14)
O2A—Ni1—N2—C10	−176.23 (9)	C11—C12—C13—C18	−3.5 (2)
O1A—Ni1—N2—C10	−154.87 (18)	C12—C13—C14—C15	−176.77 (15)
O1W—Ni1—N2—C18	−88.89 (12)	C18—C13—C14—C15	0.9 (2)
N1—Ni1—N2—C18	−177.77 (12)	C13—C14—C15—C16	−2.7 (2)
O2W—Ni1—N2—C18	89.51 (12)	C14—C15—C16—C17	1.5 (3)
O2A—Ni1—N2—C18	1.47 (13)	C15—C16—C17—C18	1.6 (2)
O1A—Ni1—N2—C18	22.8 (3)	C10—N2—C18—C17	−176.08 (13)
C9—N1—C1—C2	−178.29 (13)	Ni1—N2—C18—C17	6.36 (19)
Ni1—N1—C1—C2	4.72 (19)	C10—N2—C18—C13	2.0 (2)
C9—N1—C1—C6	0.97 (19)	Ni1—N2—C18—C13	−175.53 (10)
Ni1—N1—C1—C6	−176.03 (10)	C16—C17—C18—N2	174.87 (14)
N1—C1—C2—C3	179.38 (13)	C16—C17—C18—C13	−3.3 (2)
C6—C1—C2—C3	0.1 (2)	C12—C13—C18—N2	1.7 (2)
C1—C2—C3—C4	0.3 (2)	C14—C13—C18—N2	−176.04 (13)
C2—C3—C4—C5	−0.4 (2)	C12—C13—C18—C17	179.84 (14)
C3—C4—C5—C6	0.1 (2)	C14—C13—C18—C17	2.1 (2)
C4—C5—C6—C7	−179.25 (14)	O3A—N1A—O1A—Ni1	174.32 (12)
C4—C5—C6—C1	0.3 (2)	O2A—N1A—O1A—Ni1	−5.67 (11)
N1—C1—C6—C7	−0.1 (2)	O1W—Ni1—O1A—N1A	91.83 (8)
C2—C1—C6—C7	179.17 (13)	N1—Ni1—O1A—N1A	−178.28 (7)
N1—C1—C6—C5	−179.66 (12)	O2W—Ni1—O1A—N1A	−87.45 (8)
C2—C1—C6—C5	−0.4 (2)	N2—Ni1—O1A—N1A	−20.0 (2)
C5—C6—C7—C8	179.01 (14)	O2A—Ni1—O1A—N1A	3.54 (7)
C1—C6—C7—C8	−0.6 (2)	O3A—N1A—O2A—Ni1	−174.16 (11)
C6—C7—C8—C9	0.3 (2)	O1A—N1A—O2A—Ni1	5.84 (12)
C1—N1—C9—C8	−1.2 (2)	O1W—Ni1—O2A—N1A	−95.90 (8)
Ni1—N1—C9—C8	176.19 (11)	N1—Ni1—O2A—N1A	−12.6 (3)
C1—N1—C9—C10	−179.37 (12)	O2W—Ni1—O2A—N1A	80.51 (8)
Ni1—N1—C9—C10	−1.95 (15)	N2—Ni1—O2A—N1A	171.40 (8)
C7—C8—C9—N1	0.6 (2)	O1A—Ni1—O2A—N1A	−3.51 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2A^i	0.79 (2)	2.09 (2)	2.858 (2)	165 (2)
O1W—H1WB···O1B^i	0.84 (2)	1.90 (2)	2.733 (1)	168 (2)
O1W—H1WB···O2B^i	0.84 (2)	2.49 (2)	2.987 (2)	119 (2)
O2W—H2WA···O3A^ii	0.82 (2)	2.08 (2)	2.878 (2)	165 (2)
O2W—H2WB···O3W	0.83 (2)	1.81 (2)	2.634 (2)	173 (2)
O3W—H3WA···O2B	0.82 (3)	2.00 (3)	2.811 (2)	169 (3)
O3W—H3WB···O3B^iii	0.83 (3)	2.02 (3)	2.814 (2)	162 (3)
C2—H2···O1A	0.90 (2)	2.27 (2)	3.131 (2)	161 (2)
C17—H17···O2A	0.91 (2)	2.30 (2)	3.156 (2)	156 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+3/2.